Organic Synthesis Highlights IV Edited by Hans-Giinther Schmalz Related Titles from WILEY-VCH: J. Mulzer / H. Wuldmann (eds.) Organic Synthesis Highlights I11 1998. X. 412 pages with 302 figures Softcover. ISBN 3-527-29500-3 K. C. Nicoluou / E. J. Sorensen Classics in Total Synthesis 1996. XXIII. 792 pages with 444 figures Softcover. ISBN 3-527-2923 1-4 H. Hopf Classics in Hydrocarbon Chemistry 2000. XI. 547 pages with 434 figures Hardcover. ISBN 3-527-30216 -6 Softcover. ISBN 3-527-29606-9 J. Otera Modern Carbonyl Chemistry 2000. XX. Approx 600 pages with 542 figures and 102 tables Hardcover. ISBN 3-527-2987 1- 1 A. Ricci Modern Amination Methods 2000. Approx 400 pages Hardcover. ISBN 3-527-29976-9 J. A. Gewert et al. Problem Solving in Organic Chemistry 2000. Approx 278 pages with 284 figures Softcover. ISBN 3-527-30 187-9 Organic Synthesis Highlights IV Edited by Hans-Gunther Schmalz @WILEYVCH Weinheim . New York . Chichester . Brisbane . Singapore . Toronto Prof. Dr. Hans-Gunther Schmalz Institut fur Organische Chemie dcr Universitat zu Koln Greinstrasse 4 D-50939 Koln Germany This book was carefully produced. Nevertheless, authors, editor and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that state- ments, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No. applied for A catalogue record for this book is available from the British Library. Die Deutsche Bibliothek - CIP-Catalogning-Publication-Data A catalogue record for this publication is available from Die Deutsche Bibliothek ISBN 3-527-299 16-5 0 WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 2000 Printed on acid-free paper All rights reserved (including those of translation into other languages). No part of this book may be repro- duced in any form - by photoprinting, microfilm, or any other means - nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Composition: Mitterweger & Partner GmbH, D-68723 Plankstadt Printing: Strauss Offsetdruck GmbH, D-69509 Morlenbach Bookbinding: J. Schaffer, D-67269 Grunstadt Printed in the Federal Republic of Germany. Preface During the past century, the world has changed to and enantioselective catalysis. The second part an unprecedented extent, and the development of focuses on applications in total synthesis of nat- the chemical sciences has greatly contributed to ural products and non-natural compounds and this change. The ability of chemists to synthesize materials. In addition, a few articles reflect the complex organic molecules such as dyes, drugs, recent renaissance of solid-phase synthesis and fragrances and crop protection agents is largely the growing importance of combinatorial che- responsible for the high standard of living we mi stry. enjoy today. Moreover, synthesis as a key dis- The articles taken from “Synthese im Blick- cipline is contributing to the development of punkt” have all been carefully updated and trans- modern life sciences and materials technology. lated by the authors (U. Koert, 0. Reiser, M. However, while the power of synthesis has led Reggelin, C. Ruck-Braun). I would like to ex- to remarkable achievements, the technology press special thanks to these colleagues and their and art of organic synthesis is still far from being co-workers. I am also grateful to all the other fully developed. Many problems remain unsolved authors for their excellent and up-to-date contri- concerning, for instance, the efficiency and butions. I also have to thank the team at Wiley- atom-economy of syntheses. Organic synthesis VCH, especially Dr. A. Eckerle, Dr. G. Walter, continues to offer multifarious academic and Dr. A. Kessinger and P. Biel for their excellent, technological challenges, and a tremendous professional support and their patience with the amount of research is carried out worlwide in editor. this field. I hope this new volume will find as much This fourth volume of Organic Synthesis High- acceptance in the scientific community as the lights (OSH) comprises a collection of more first three volumes of this series and will help than 40 articles reflecting some more recent de- to stimulate the interest of, in particular, young velopments and achievements of organic synth- chemists in the field of synthesis. esis. About half of the contributions have their origin in the review section “Synthese im Blick- Cologne, February 2000 punkt” in Nachrichten aus Chemie, Technik Hans-Giinther Schmalz und Labnratorium (1994- 1998), the members’ journal of the GDCh; most of the others have been selected from the “Highlights” of An- gewandte Chemie (1997- 1998). The first half of the present volume concerns synthetic metho- dology, with emphasis on stereoselective synth- esis, transition metal organometallic methods, Contents Part I. Synthetic Methods A. New Methods in Stereoselective Synthesis Stereocontrolled Simmons-Smith Cyclopropanation .............................. 3 Julia Schuppan and Ulrich Koert Oppolzer Sultams ...................................................... 11 Oliver Reiser Oxazolines: Chiral Building blocks, Auxiliaries and Ligands ........................ 17 Martin Glos and Oliver Reiser New Sequential Reactions with Single Electron Transferring Agents ................... 34 Troels Skrydstrup Deracemisation by Enantiodifferentiating Inversion in 1,3- and I ,2-Diols ............... 40 Anthony I? Davis Non-Biaryl Atropisomers: New Classes of Chiral Reagents, Auxiliaries and Ligands? ...... 48 Jonathan Clayden Amino Acid Derivatives by Multicomponent Reactions ............................ 53 Gerald Dyker New Polyol Syntheses ................................................... 58 Christoph Schneider Stereoselection at the Steady State: The Design of New Asymmetric Reactions ........... 67 Thomas Wirth, B. Transition Metal Organometallic Methods Photolysis of Fischer Carbene Complexes ..................................... 7 1 Oliver Kiehl and Hans-Gunther Schmalz Zr-Catalyzed Carbomagnesation of Alkenes .................................... 77 Florian Blume and Hans-Gunther Schmalz VIII Contents Intramolecular Alkoxypalladation .......................................... 83 Oliver Geis and Hans-Giinther Schmalz Ring-closing Olefin Metathesis ............................................ 91 Michael Kurle and Ulrich Koert Metal-Catalyzed Hydroformylations ........................................ 97 Oliver Reiser Rare Earth Metal Catalysts .............................................. 104 Patrick Amrhein and Kurola Ruck-Bruun Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: New and Efficient Carbonyl Olefination ..................................... 110 Bernhurd Breit New Developments in the Pauson-Khand Reaction .............................. 116 Oliver Geis and Huns-Giinther Schmalz Multicomponent Catalysis for Reductive Bond Formations ........................ 123 Alois Fiirstner Natural Product Synthesis by Rh-mediated Intramolecular C-H Insertion .............. 130 Douglass I? Taber and Suluh-E. Stiriba C. Enantioselective Catalysis Enantioselective Heck Reactions ........................................... 136 Marku.5 Jachmann and Hans-Giinther Schmalz Catalytic Asymmetric Aldol Reactions ...................................... 144 Rolf Krauss and Ulrich Koert Binaphthyls: Universal Ligands for Catalysis .................................. I55 Tobias Wubnitz and Oliver Reiser Fluorotitanium Compounds - Novel Catalysts for the Addition of Nucleophiles to Aldehydes ........................................................ 166 Rudolf 0. Duthaler and Andreas Hufner Enzymes and Transition Metal Complexes in Tandem - a New Concept for Dynamic Kinetic Resolution .................................................... 172 Ruiner Stiirmer Non-Enzymatic Kinetic Resolution of Secondary Alcohols ........................ 175 Peter Somfai Copper-Catalyzed Enantioselective Michael Additions: Recent Progress with New Phosphorus Ligands ................................................... 182 Norbert Krause C,-Symmetric Ligands for Catalysis ........................................ 187 Mark Mikula's and Kurola Ruck-Bruun Highly Enantioselective Catalytic Reduction of Ketones Paying Particular Attention to Aliphatic Derivatives ................................................... 194 Renat Kadyrov and Riidiger Selke Contarits IX Part 11. Applications A. Total Synthesis of Natural Products Total Synthesis of Ikarugamycin ........................................... 207 Oliver Schwarz and Hans-Gunther Schmulz Palladium-Catalyzed Synthesis of Vitamin D-Active Compounds .................... 2 I2 Sandra Kruuse and Huns-Gunther Schmnlz Syntheses of Oligo(thiazo1ine) Natural Products ................................ 2 18 Subine Hoppen and Ulrich Koert Camptothecin - Synthesis of an Antitumor Agent ............................... 232 Stcfun Biiurle and Ulrich Koert Polycyclic Guanidines From Nature's Shaped Cations to Abiotic Anion Hosts ........... 241 Hans-Dieter Arndt und Ulrich Koert Synthetic Access to Epothilones - Natural Products with Extraordinary Anticancer Activity . 25 I Ludger A. Wessjohunn und Giinther Scheid Total Syntheses of the Marine Natural Product Eleutherobin ....................... 268 Thonius Lindel Selectin Inhibitors ..................................................... 275 Murkiis Riisch und Kurola Riick-Bruun Crossing the Finishing Line: Totdl Syntheses of the Vancomycin Aglycon .............. 281 Holger Herzner and Kurola Riick-Braun B. Synthesis of Non-Natural Compounds and Materials An Update on the New Inductees in the ,,Hall of Phane" - No Phane, No Gain! ......... 289 Graham -1. Bodwell Well-Rounded Research: Nanotubes through Self-Assembly ........................ 30 1 Burkhurd Kiinig From Random Coil to Extended Nanocylinder: Dendrimer Fragments Shape Polymer Chains 306 Holger Frey C. Solid Phase Synthesis and Combinatorial Chemistry Combinatorial Methods - Prospects for Catalysis? .............................. 3 I4 Reinhard Racker and Oliver Reiser The Renaissance of Soluble Polymers ....................................... 322 M. Reggelin Polymeric Catalysts .................................................... 328 M. Reggelin Combinatorial Chemistry for the Synthesis of CarbohydrateKarbohydrate Mimics Libraries . 337 Prubhat Arya, Robert N. Ben and Kristina M. K. Kutterer Combinatorial Biosynthesis of Polyketides .................................... 343 Kui Donsbuch and Kamla Ruck-Braun Index .............................................................. 351 List of Contributors Dr. P. Arya Prof. Dr. G. Dyker Steacie Inst. f. Mol. Sciences FB6-Inst. f. Synthesechemie Nat. Research Council of Canada der Universitat-GH Duisburg 100 Sussex Drive Lotharstr. I CanadaKlA OR6 Ottawa 47048 Duisburg Dr. G. J. Bodwell Dr. H. Frey Department of Chemistry Inst. fur Makromolek. Chemie Memorial University of NF (FMF), Universitat Freiburg KanadaAlB 3x7 St. John’s Stefan-Meier Str. 21/31 Priv.-Doz. Dr. B. Breit Prof. Dr. A. Fiirstner Organisch-Chemisches Institut Max-Planck-Institut der Universitat Heidelberg fur Kohlenforschung Im Neuenheimer Feld 270 Kaiser-Wilhelm-Platz I 69120 Heidelberg 45470 Miilheim Dr. J. P. Clayden Prof. Dr. N. Krause Department of Chemistry Lehrst. fur Organische Chemie University of Manchester Universitat Dortmund Oxford Rd. 44221 Dortmund M13 9PL Manchester Prof. Dr. U. Koert Institut fur Chemie Prof. A. P. Davis Department of Chemistry der Humboldt-Universitat (University of Dublin Hessische Str. 1-2 Trinity College 10115 Berlin Ir-2 Dublin Prof. Dr. B. Konig Dr. R. Duthaler Inst. fur Organische Chemie Novartis Pharma AG der Universitat Regensburg WSJ-507.109 Universitatsstr. 3 1 Postfach 93053 Regensburg 4002 Base1 XI1 List of Contributors Dr. T. Lindel Prof. Dr. T. Skrydstrup Pharmazeut.-chem. Institut Department of Chemistry der Universitat Heidelberg University of Aarhus Im Neuenheimer Feld 364 Langelandsgade I40 69 120 Heidelberg DK-8000 AarhudDenmark Dr. M. Reggelin Prof. Dr. R. Selke Institut fur Organische Chemie Ifok, ,,Asymmetrische Katalyse" Universitat Mainz an der Universitat Rostock Dusbergweg 10- 14 Buchbinderstr. 5-6 55099 Mainz 18055 Rostock Prof. Dr. 0. Reiser Dr. P. Somfai Institut fur Organische Chemie Dept. of Organic Chemistry der Universitat Regensburg Stockholm University Universitatsstr. 3 1 Arrhenius Laboratory 93053 Regensburg 10691 StockholmE Dr. R. Sturmer BASF AG Dr. K. Ruck-Braun Hauptlaborat., ZHF/D A30 Institut f. Organische Chemie 67056 Ludwigshafen J. Gutenberg-Universitat Mainz Duesbergweg 10- 14 Prof, Dr. D. F. Taber 55099 Mainz Dept. of Chemistry and Biochemistry Prof. Dr. H.-G. Schmalz University of Delaware Inst. fur Organische Chemie USA 197 16 Newark Universitat Koln GreinstraRe 4 Prof. Dr. L. A. Wessjohann 50939 Koln Faculty of Chemistry (N 348) Vrije Universiteit Amsterdam Dr. C. Schneider de Boelelaan 1083 Institut fur Organische Chemie HV 1081 Amsterdam der Universitat Tammannstr. 2 PD Dr. T. Wirth 37077 Gottingen Institut fur Organische Chemie Universitat Basel St. Johanns-Ring 19 4056 Basel